RESUMO
Tailoring the Li+ microenvironment is crucial for achieving fast ionic transfer and a mechanically reinforced solid-electrolyte interphase (SEI), which administers the stable cycling of Li-metal batteries (LMBs). Apart from traditional salt/solvent compositional tuning, this study presents the simultaneous modulation of Li+ transport and SEI chemistry using a citric acid (CA)-modified silica-based colloidal electrolyte (C-SCE). CA-tethered silica (CA-SiO2 ) can render more active sites for attracting complex anions, leading to further dissociation of Li+ from the anions, resulting in a high Li+ transference number (≈0.75). Intermolecular hydrogen bonds between solvent molecules and CA-SiO2 and their migration also act as nano-carrier for delivering additives and anions toward the Li surface, reinforcing the SEI via the co-implantation of SiO2 and fluorinated components. Notably, C-SCE demonstrated Li dendrite suppression and improved cycling stability of LMBs compared with the CA-free SiO2 colloidal electrolyte, hinting that the surface properties of the nanoparticles have a huge impact on the dendrite-inhibiting role of nano colloidal electrolytes.
RESUMO
To recharge lithium-ion batteries quickly and safely while avoiding capacity loss and safety risks, a novel electrode design that minimizes cell polarization at a higher current is highly desired. This work presents a dual-layer electrode (DLE) technology via sequential coating of two different anode materials to minimize the overall electrode resistance upon fast charging. Electrochemical impedance spectroscopy and distribution of relaxation times analysis revealed the dynamic evolution of electrode impedances in synthetic graphite (SG) upon a change in the state of charge (SOC), whereas the natural graphite (NG) maintains its original impedance regardless of SOC variation. This disparity dictates the sequence of the NG and SG coating layers within the DLE, considering the temporal SOC gradient developed upon fast charging. Simulation and experimental results suggest that DLE positioning NG and SG on the top (second-layer) and bottom (first-layer), respectively, can effectively reduce the overall resistance at a 4 C-rate (15-min charging), demonstrating two times higher capacity retention (61.0%) over 200 cycles than its counterpart with reversal sequential coating, and is higher than single-layer electrodes using NG or NG/SG binary mixtures. Hence, this study can guide the combinatorial sequence for multi-layer coating of various active materials for a lower-resistivity, thick-electrode design.
RESUMO
Despite the promises in high-energy-density batteries, Li-metal anodes (LMAs) have suffered from extensive electrolyte decomposition and unlimited volume expansion owing to thick, porous layer buildup during cycling. It mainly originates from a ceaseless reiteration of the formation and collapse of solid-electrolyte interphase (SEI). This study reveals the structural and chemical evolutions of the reacted Li layer after different cycles and investigates its detrimental effects on the cycling stability under practical conditions. Instead of the immediately deactivated top surface of the reacted Li layer, the chemical nature underneath the reacted Li layer can be an important indicator of the electrolyte compositional changes. It is found that cycling of LMAs with a lean electrolyte (≈3 g Ah-1 ) causes fast depletion of salt anions, leading to the dynamic evolution of the reacted Li layer structure and composition. Increasing the salt-solvent complex while reducing the non-solvating diluent retards the rate of depletion in a localized high-concentration electrolyte, thereby demonstrating prolonged cycling of Li||NMC622 cells without compromising the Li Coulombic efficiencies and high-voltage stability.